JP2007210175A - Laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film of a polybutylene terephthalate resin and a poly 4-methyl-1-pentene resin having both of mold releasability and shape followability. <P>SOLUTION: The laminated film is composed of the polybutylene terephthalate resin (C) constituted by adding 0.8-52 pts.wt. of an epoxy group-containing olefinic resin (B) to 100 pts.wt. of the polybutylene terephthalate resin (A) and the poly 4-methyl-1-pentene resin (D). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated film that maintains properties excellent in releasability and shape followability and is excellent in extrudability.

  Thermoplastic polyester resins, especially polybutylene terephthalate resin (hereinafter abbreviated as “PBT” if necessary), have properties suitable as engineering plastics such as excellent heat resistance, moldability, chemical resistance and electrical insulation. Therefore, it is used for various automobile parts, electrical parts, machine parts, construction parts, etc. mainly for injection molding.

  In recent years, application in the field of film applications that takes advantage of the barrier properties, heat resistance, shape retention performance, etc. of PBT has attracted attention. However, PBT resin does not have sufficient releasability and has unsatisfactory uses.

  In addition, the poly-4-methyl-1-pentene film has been developed for applications utilizing the characteristics of heat resistance, transparency, gas permeability, and releasability, but the shape following property is not good. There was a drawback.

  That is, it has been desired to produce a laminated film that compensates for these drawbacks.

  In order to solve the above problem, for example, Patent Document 1 discloses a film in which a silicone release layer is provided on polyester. However, there are two types of silicone resins, thermosetting type and ultraviolet curing type. Even if the type of resin and the curing method are changed, it is difficult to completely cure and adhere the coating film. Shifting to a product that comes into contact has been a challenge.

On the other hand, since polyester and poly-4-methyl-1-pentene have poor adhesion, they do not adhere to each other even when two layers are coextruded. Patent Documents 2 to 4 disclose a method in which an adhesive resin is interposed between a resin containing poly-4-methyl-1-pentene resin and polyester, but shape followability is inferior due to the influence of the intermediate layer. The problem that occurred.
JP 2005-138339 A JP 2000-218752 A JP-A-9-268243 Japanese Patent Laid-Open No. 2-107438

  The present invention aims to further improve the above prior art. That is, the present invention provides a laminated film of polybutylene terephthalate resin and poly-4-methyl-1-pentene resin having both releasability and shape followability.

As a result of diligent research to solve the problems of the prior art, the present inventors have completed the present invention. The object of the present invention is polybutylene terephthalate resin and poly-4-methyl-1-pentene. It is a laminated film that takes advantage of the properties of the resin. That is,
(1) A polybutylene terephthalate resin composition (C) obtained by blending 0.8 to 52 parts by weight of an epoxy group-containing olefin resin (B) with respect to 100 parts by weight of a polybutylene terephthalate resin (A), A laminated film of 4-methyl-1-pentene resin (D),
(2) The laminated film according to the above (1), wherein the intrinsic viscosity of the polybutylene terephthalate resin (A) is 0.7 to 1.9,
(3) The laminated film according to the above (1) or (2), wherein the epoxy group-containing olefin resin (B) is ethylene-glycidyl methacrylate,
(4) The epoxy group-containing olefin resin (B) is ethylene-glycidyl methacrylate, and when the total epoxy group-containing olefin resin (B) is 100% by weight, the proportion of ethylene is 65 to 97% by weight, glycidyl methacrylate. The laminated film according to any one of (1) to (3), wherein the ratio of
(5) The MFR of the poly-4-methyl-1-pentene resin (D) is 0.5 to 200 g / 10 min as measured at 260 ° C., 5 minutes retention, and 5 kg load. ) Laminated film according to any one of
(6) The method for producing a laminated film according to any one of (1) to (5) above, wherein (C) and (D) are coextruded.
(7) The method for producing a laminated film according to any one of (1) to (5) above, wherein (C) and (D) are non-stretched and extruded.
(8) A release film comprising the laminated film according to any one of (1) to (5) is provided.

  A laminated film having both the characteristics of the polybutylene terephthalate resin and the poly-4-methyl-1-pentene resin of the present invention can be obtained.

  The present invention is described in detail below.

  The polybutylene terephthalate resin (A) used in the present invention is a normal polymerization such as a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. It is a polymer obtained by the method and may contain other copolymerization components in a range that does not impair the characteristics, for example, about 20% by weight or less. Preferred examples of these (co) polymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene ( Terephthalate / naphthalate), poly (butylene / ethylene) terephthalate, and the like. These may be used alone or in combination.

The intrinsic viscosity of polybutylene terephthalate is preferably 0.7 to 1.9, more preferably 0.8 to 1.85, and still more preferably 1.2 to 1.8. If the intrinsic viscosity is less than 0.7, the film formability deteriorates, and if it is greater than 1.9, the load on the extruder increases, which is not preferable.
Examples of the olefin of the epoxy group-containing olefin resin (B) of the present invention include ethylene, propylene, 1-butene, and specific examples of the epoxy group-containing unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, Glycidyl ester obtained by copolymerizing glycidyl ethacrylate, glycidyl itaconate, etc., and vinyl esters such as vinyl ethers, vinyl acetate and vinyl propionate, and acrylic and methacrylic esters such as methyl, ethyl, propyl and butyl. -Tells and glycidyl esters are mentioned, and specific examples of the epoxy group-containing olefin resin (B) include ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methacrylic acid. Methyl / Methacrylic acid glycidyl copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, and an ethylene / glycidyl ether copolymers. Of these, an ethylene / glycidyl methacrylate copolymer is most preferred. The proportion of ethylene and glycidyl methacrylate is preferably 65 to 97% by weight of ethylene and 3 to 35% by weight of glycidyl methacrylate, more preferably 80 to 95% by weight of ethylene, 5 to 20% by weight of glycidyl methacrylate, and still more preferably 85 to 85% of ethylene. 88 wt%, glycidyl methacrylate 12 wt% to 15 wt%. When the proportion of glycidyl methacrylate is less than 3% by weight, sufficient adhesion with 4-methyl-1-pentene resin is not recognized, and when it exceeds 35% by weight, the reaction with PBT accelerates and the viscosity increases. It is not preferable.

  Further, the epoxy group-containing olefin resin (B) is effective even with a ternary copolymer, and among them, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer are preferable, More preferred is an ethylene / methyl acrylate / glycidyl methacrylate copolymer.

  The amount of the epoxy group-containing olefin resin (B) added is preferably 0.8 to 52 parts by weight, particularly 2 to 10 parts by weight, when the polybutylene terephthalate resin (A) is 100 parts by weight. If it is less than 0.8 part by weight, the adhesive strength with poly-4-methyl-1-pentene resin is poor, and if it exceeds 52 parts by weight, the characteristics inherent to PBT (barrier properties, heat resistance, shape retention) are impaired. Absent.

  The poly-4-methyl-1-pentene resin (D) of the present invention is a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and α-olefin. Here, the α-olefin to be copolymerized with 4-methyl-1-pentene is an olefin having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene. 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc., and these may be used alone or in combination of two or more. The α-olefin is contained in the copolymer in an amount of 0 to 20 mol%, preferably 0 to 15 mol%.

  The poly-4-methyl-1-pentene resin is not particularly limited as long as the poly-4-methyl-1-pentene resin has a molecular weight exhibiting sufficient fluidity to form a film and sufficient mechanical strength as a film. The flow rate) is 0.5 to 200, preferably 5 to 120 (g / 10 min). In addition, MFR is a value measured under 260 degreeC, 6 minute residence, and 5 kg load based on ASTMD1238.

Such poly-4-methyl-1-pentene resin can be produced by a known method by using a Ziegler-Natta catalyst or a metallocene catalyst.
Further, the polybutylene terephthalate resin or poly-4-methyl-1-pentene resin of the present invention includes a reinforcing material, a filler, an antioxidant, a stabilizer, an ultraviolet absorber, and a colorant as long as the effects of the present invention are not impaired. Ordinary additives such as mold release agents and flame retardants and small amounts of other polymers can be added.

  Stabilizers include benzotriazole compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and benzophenone compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, trimethyl phosphate And phosphoric acid esters.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. That is, the above classification is for convenience and does not limit the action.

Release agents include plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and polyethylene wax, castor oil and its Derivatives, fatty acids, and oil-based waxes such as derivatives thereof. Examples of higher fatty acid derivatives include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and montanic acid, and monohydric or dihydric or higher alcohols. Esters, partial saponification of these higher fatty acid esters partially with metal oxides such as Ca (OH) ₂ , NaOH, Mg (OH) ₂ , Zn (OH) ₂ , LiOH, Al (OH) ₃ Saponification obtained from esterified esters, higher fatty acids and metal oxides or metal hydroxides Products, higher fatty acids and polyhydric alcohol esters, which are condensed with a dicarboxylic acid such as adipic acid as a binder, mono- or diamides obtained from higher fatty acids and monoamines or diamines.

  Among the flame retardants, the brominated flame retardant is indispensable for imparting flame retardancy. Specific examples of the brominated flame retardant include halogenated polycarbonate (for example, tetrabromobisphenol A carbonate oligomer), halogenated acrylic resin, halogenated epoxy resin, halogenated phenoxy resin, halogenated polystyrene, tetrabromobisphenol A / ethyl. High molecular weight organic halogen compounds such as ether oligomers and halogenated polyphenylene ethers (eg, polydibromophenylene oxide); Decabromodiphenyl ether, hexabromophenol, tetrabromobisphenol A, epoxidized tetrabromobisphenol A, tetrabromobisphenol A / bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (allyl ether), tetrabromobisphenol A. Brominated bisphenol A such as 2-hydroxyethyl ether, hexabromobenzene, tetrabromophthalic anhydride, tribromophenol, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane, ethylenebistetrabromophthalimide, bromine And low molecular weight organic halogen compounds such as bis (2,3-dibromopropyl ether) of tetrabromobisphenol S and tetrabromobisphenol S. These organic halogen flame retardants can be used alone. Also, two or more of them may be used in combination. Moreover, phosphorus-based and inorganic flame retardants can also be used. As various polymers, polycarbonate resin, polyethylene terephthalate resin, nylon resin, PPS resin, polytetrafluoroethylene and the like can be added.

  What is necessary is just to implement about the manufacturing method of the polybutylene terephthalate resin composition for films of this invention by the method generally known, and does not need to specifically limit. A typical example is a method of melt-kneading at a temperature of 200 to 350 ° C. using a known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Each component may be mixed in advance and then melt kneaded. Alternatively, with respect to 100 parts by weight of component (C), for a small amount of additive component such as 1 part by weight or less, other components may be kneaded and pelletized by the above method and then added before molding. it can. In addition, although it is better that the water | moisture content adhering to each component is less and it is desirable to dry beforehand, not all the components need to be dried.

  The resin of the present invention can produce a film by extrusion with a T-die or inflation. Among them, co-extrusion with a T-die is a laminated film of polybutylene terephthalate resin and poly-4-methyl-1-pentene resin. The best way to manufacture. Thereby, a laminated | multilayer film can be created at once.

  The thickness of the film of the present invention is not particularly limited as long as the polybutylene terephthalate film and the poly-4-methyl-1-pentene film are each between 5 and 500 μm.

  The laminated film of the present invention is excellent in heat resistance, chemical resistance, electrical insulation, releasability, and shape followability, and can be widely used for applications such as heat resistant film, release film, and electrical insulation film.

Hereinafter, the present invention will be described in more detail with reference to examples. The compounding compositions used in Examples and Comparative Examples are shown below.
(Aa) Polybutylene terephthalate resin Intrinsic viscosity 1.74 PBT resin “Toraycon” 1400S manufactured by Toray Industries, Inc.
(Ab) Polybutylene terephthalate resin Intrinsic viscosity 1.26 PBT resin “Toraycon” 1200S manufactured by Toray Industries, Inc.
(Ac) Polybutylene terephthalate resin Inherent viscosity 0.85 PBT resin “Toraycon” 1100S manufactured by Toray Industries, Inc.
(Ba) Ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer (Bond First-E manufactured by Sumitomo Chemical Co., Ltd.)
(Bb) Ethylene / glycidyl methacrylate = 80/20 (wt%) copolymer This copolymer is composed of 80 wt% ethylene and 20 wt% glycidyl methacrylate, and 1,3-bis (t -Butylperoxyisoprovir) After 0.5 parts by weight of benzene and 0.1 parts by weight of IR1010 (manufactured by Ciba Geigy) as a stabilizer were uniformly mixed with a Henschel mixer, the temperature was 270 ° C. with a 120 mφ twin-screw extruder. (Bc) Ethylene homopolymer (Ultra Zex 2005HC manufactured by Mitsui Chemicals, Inc.) obtained by melt-kneading with an average residence time of 0.8 minutes and copolymerization
(Bd) Copolymer of ethylene / glycidyl methacrylate = 70/30 (wt%) This copolymer is composed of 70 wt% of ethylene and 20 wt% of glycidyl methacrylate, and 1 · 3-bis (t -Butylperoxyisoprovir) After 0.5 parts by weight of benzene and 0.1 parts by weight of IR1010 (manufactured by Ciba Geigy) as a stabilizer were uniformly mixed with a Henschel mixer, the temperature was 270 ° C. with a 120 mφ twin-screw extruder. (Be) ethylene / glycidyl methacrylate = 94/6 (% by weight) copolymer (ETX6 manufactured by Sumitomo Chemical Co., Ltd.) obtained by melt-kneading with an average residence time of 0.8 minutes and copolymerization
(Bf) ethylene / methyl acrylate / glycidyl methacrylate = 64/30/6 (% by weight) copolymer (bond first 7M, manufactured by Sumitomo Chemical Co., Ltd.)
(D-a) 4-Methyl-1-pentene resin (MFR 21 g / 10 min) (RT31 manufactured by Mitsui Chemicals)
(Db) 4-Methyl-1-pentene resin (MFR 180 g / 10 min) (DX820, Mitsui Chemicals)
(I) Shape followability is followed by pressing the prepared laminated film against a square pyramid metal piece with a side of 10 mm and a height of 5 mm, and then peeling off the film to confirm the followability. If it is, ○, and if the corners are rounded, it is ×.
(ii) Regarding the adhesive strength of the films of (C) and (D), a test piece of 50 mm × 10 mm was prepared, and after the film was prepared, it was allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours. I peeled it off. If it was not peeled off, it was marked as x when it was peeled off by two surface layers.

[Examples 1 to 10]
The components (A) and (B) were mixed at room temperature in the proportions shown in Table 1, and melt-kneaded using a twin screw extruder ZSK57 having a screw diameter of 57 mmφ. The supply of the component (A) and the component (B) was performed from the extruder feed-in portion, and the cylinder temperature was set to 250 ° C. The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter to obtain component (C), which was dried with a hot air dryer at 130 ° C. for 3 hours or more. Next, the component (C) obtained and the component (D) described in Table 1 were prepared. The component (C) was set at a cylinder temperature of 250 ° C., the component (D) was set at a cylinder temperature of 290 ° C. Co-extrusion was performed with a film forming apparatus, and a two-layer laminated film was prepared and evaluated. The film forming apparatus used was a single screw extruder VS40-25 manufactured by Shinko Machinery Co., Ltd., and the screw used was a two-layer T-die with a full flight constant pitch and a compression ratio of 3. The film thicknesses of component (C) and component (D) were 100 μm, respectively.

  The results are shown in Table 1. All of the obtained films were good in both shape followability and adhesive strength between the two layers (C) and (D).

[Example 11]
Example 1 except that (A) component and (B) component were not melt-kneaded using an extruder and (A) component and (B) component were mixed at room temperature to obtain (C) component. Similarly, a laminated film was prepared and evaluated.

  The results are shown in Table 1. The obtained film was good in both shape followability and adhesive strength between the two layers (C) and (D).

[Comparative Examples 1-4]
A laminated film was prepared and evaluated in the same manner as in Example 1 except that the composition shown in Table 1 was used. The results are shown in Table 1. When an olefin without an epoxy group is used as the component (B) (Comparative Example 1), when only the component (A) is used (Comparative Example 2), the component (A) When a small amount of the component (B) was added (Comparative Example 3), the adhesive force between the component (C) and the component (D) was insufficient. On the other hand, when a large amount of the component (B) was added to the component (A), the shape followability was insufficient (Comparative Example 4).

[Comparative Example 5]
(Aa) was dried with a hot air dryer at 130 ° C. for 3 hours or more, and extruded at a cylinder temperature of 250 ° C. with the following film forming apparatus to prepare a single layer laminated film. A single-screw extruder VS40-25 manufactured by Shinko Machinery Co., Ltd. was used as the film forming apparatus, and a single-layer T-die was used as the screw with a full flight constant pitch and a compression ratio of 3. The film thickness of the component (C) was 100 μm. The resulting 100 μm polybutylene terephthalate resin film was coated with an acrylic group-containing silicon compound by vacuum film formation and cured with an electron beam of 20 Mrad. As a result of actually using the obtained film, a problem of shifting to a product to which a silicon-based coating film adheres occurred. This is a phenomenon not seen in the films obtained in Examples 1-11.

[Comparative Example 6]
Ethylene / propylene random copolymer (ethylene content 80 mol, MFR 21.2 g / 10 min, specific gravity 0.88, crystallinity 6%) and maleic anhydride grafted high density polyethylene (maleic anhydride graft) as intermediate layer materials 2.1 g / 100 g polymer, MFR 32.4 g / 10 min, specific gravity 0.96, crystallinity 76%) and alicyclic hydrogenated petroleum resin (tackifier: trade name Alcon P125, softening point 125 ° C., bromine No. 2 (produced by Arakawa Chemical Co., Ltd.) was mixed with a tumbler at a ratio of 88/2/10, and kneaded and granulated with a single screw extruder (Dalmage screw, 40 mmΦ) set at 200 ° C. The obtained material for the intermediate layer, (Aa) dried for 3 hours or more with a 130 ° C. hot air dryer, and (Da) were coextruded with a three-layer T-die film extruder. . The film forming apparatus used was a single screw extruder VS40-25 manufactured by Shinko Machinery Co., Ltd., and the screw was a three-layer T-die with a full flight constant pitch and a compression ratio of 3. Although the adhesive strength of the obtained film was sufficient, the process was complicated in that a three-layer T-die was required, and the problem of poor shape following occurred due to the influence of the intermediate layer.

Claims (8)

A polybutylene terephthalate resin composition (C) comprising 0.8 to 52 parts by weight of an epoxy group-containing olefin resin (B) to 100 parts by weight of a polybutylene terephthalate resin (A), and poly-4-methyl -1- Laminated film of pentene resin (D). The laminated film according to claim 1, wherein the polybutylene terephthalate resin (A) has an intrinsic viscosity of 0.7 to 1.9. The laminated film according to claim 1 or 2, wherein the epoxy group-containing olefin resin (B) is ethylene-glycidyl methacrylate. The epoxy group-containing olefin resin (B) is ethylene-glycidyl methacrylate, the proportion of ethylene is 65 to 97 wt% when the total epoxy group-containing olefin resin (B) is 100 wt%, and the proportion of glycidyl methacrylate is The laminated film according to any one of claims 1 to 3, which is 3 to 35% by weight. 5. The MFR of the poly-4-methyl-1-pentene resin (D) is 0.5 to 200 g / 10 min as measured under 260 ° C., 5-minute residence, and 5 kg load. Laminated film. The method for producing a laminated film according to claim 1, wherein (C) and (D) are coextruded. The method for producing a laminated film according to any one of claims 1 to 5, wherein (C) and (D) are non-stretched and extruded. A release film comprising the laminated film according to claim 1.